This invention relates to heteroporphyrin nanostructures comprising metalloporphyrin coordination polymers.
Abrahams and coworkers reported the formation of 3D polymeric network of Pd-tetra(4-pyridyl)porphyrin (Pd-T(4-Py)P) connected through trans-coordination of pyridyl nitrogens to Cd(NO3)2(H2O)2 moieties that were formed in boiling 1:1 methanol:water+boiling ethanol. Crystals suitable for X-ray diffraction analysis precipitated upon cooling. (B. F. Abrahams, B. F. Hoskins, and R. Robson, “A New Type of Infinite 3D Polymeric Network Containing 4-centered, Peripherally Linked Metalloporphyrin Building Blocks,” J. Amer. Chem. Soc. (1991) vol. 113, pp. 3606-3607.)
Pan et al. reported formation of Hg(H2TPyP) microcrystalline solid by combination of a methanol solution of HgBr2 and a chloroform solution of H2TPyP. Slow precipitation produces plate-like crystals suitable for X-ray analysis. (L. Pan, B. C. Noll, and X. Wang, “Self-Assembly of free-base tetrapyridylporphyrin units by metal ion coordination,” Chem. Commun. (1999) pp. 157-158.)
Sharma and coworkers have reported coordination complexes of metal halides (MX2 (M=Cd, Hg, Pb; X=Br, I) with freebase tetrapyridylporphyrin (TPyP) that form either 1-D [(HgX2)2TPyP].2TCE or 2-D [(MX2)TPyP]·4 TCE (M=Pb, Cd) where TCE is 1,1,2,2-tetrachloroethane. The TPyP was metalated with Zn2+, Cu2+, and Ni2+. The single crystals of TPyP coordination polymers (freebase, partially and fully metallated) were grown using a layering technique at ambient temperatures in which TPyP was dissolved in 3:1 solution mixtures of TCE and methanol and then layered with metal salts dissolved in methanol. (C. V. K. Sharma, G. A. Broker, J. G. Huddleston, J. W. Baldwin, R. M. Metzger, and R. D. Rogers, “Design Strategies for Solid-State Supramolecular Arrays Containing Both Mixed-Metalated and Freebase Porphyrins,” J. Amer. Chem. Soc. (1999) vol. 121, pp. 1137-1144.)
Krupitsky and coworkers have described the formation of oligomers involving pyridine meso-substituted porphyrins axially coordinated to the metal ion center of adjacent metalloporphyrin molecules. Coordination polymers form through ligation of the porphyrin periphery on one molecule to the metal center of an adjacent porphyrin. (H. Krupitsky, Z. Stein, I. Goldberg, and C. H. Strouse, “Crystalline Complexes, Coordination Polymers, and Aggregation Modes of Tetra(4-pyridyl)porphyrin,” J. Inclusion Phenomena and Molecular Recognition in chemistry (1994) vol. 18, pp. 177-192.)
Drain and coworkers report the formation of nanoscale colloidal particles of hydrophobic porphyrins such as 5,10,15,20-tetraphenylporphyrin (TPP), 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) and the metallo derivatives by adding water (guest solvent) to a solution of the hydrophobic porphyrin in THF, DMSO, DMF, or CH3CN (host solvent) with a few percent of a low molecular weight PEG such as HO(C2H4O)4CH3 or a non-ionic surfactant. Stabilizers such as PEG are essential for the formation of stable colloidal systems by host-guest solvent methods. The rate an efficiency of mixing the host and guest solvents have a profound effect on the size and stability of the porphyrinic nanoparticles-especially when metalloporphyrins are used. In general for a given derivative and using the same rate of addition, the greater the mixing the small the nanoparticles. The size of the colloidal particles of free base TPP decreases in the order: no stirring, a magnetic stir-bar with a vortex, a vortex mixer, and sonication. ‘Stable metalloporphyrin particles are generally formed only when sonication is used. (C. M. Drain, G. Smeureanu, S. Patel, X. Gong, J. Garno, and J. Arijeloye, “Porphyrin nanoparticles as supramolecular systems,” New Journal of Chemistry (2006) vol. 30, pp. 1834-1843).
Diskin-Posner and co-workers have reported that metalated 5,10,15,20-tetraphenylporphyrins can be axially linked to each other with the aid of amine and diamine ligands. Seven crystalline materials consisting of such heterogeneous coordination oligomers and polymers of Zn(II)— or Mn(II)-tetraphenylporphyrins have been prepared and characterized by X-ray crystallography. Ligands of varying length have been used as bridging auxiliaries between the metal centers of the porphyrin species. A homogenous coordination polymer of Zn(II)-tetrapyridylporphyrin derivative was also reported. The polymeric arrays in this compound are composed of two crystallographically independent porphyrin units oriented perpendicularly to one another, one with a five-coordinated and the other with a six-coordinated zinc ion. They are arranged in an alternating manner along the polymer. Every building block has three connections to the neighboring molecules. The six-coordinated porphyrin links axially to two five-coordinated species located on opposite sides of its planar core ring, and laterally through one of its pyridyl rings to another five-coordinate moiety. Simultaneously, every five-coordinate molecule associates with three six-coordinate porphyrins through two of its trans-related pyridyl rings as well as by attracting the pyridyl group of another unit to its central zinc ion. (Y. Diskin-Posner, G. K. Patra, and I. Goldberg, “Supramolecular assembly of metalloporphyrins in crystals by axial coordination through amine ligands,” J. Chem. Soc., Dalton Trans., (2001) pp. 2775-2782.)
Yuan and coworkers have reported the synthesis of multiporphyrin and porphyrin-viologen assemblies linked in square planar arrays by Pd(II) or Pt(II) ions. The porphyrins used in their work are monopyridyltriarylporphyrins and the corresponding Zn-substituted monopyridyltriaryl porphyrin. Pyridyl porphyrin metal complexes with a d8 metal ion coordinated to the pyridyl nitrogen can be readily synthesized by treating the appropriate porphyrin with M(DMSO)2Cl2 (M=Pt, Pd) in refluxing CHCl3. The complexes remain intact in solution for weeks and in the solid state for more than one year. Replacement of the second DMSO ligand requires slightly higher reaction temperatures; treating with a second equivalent of (PyPP))H2 in refluxing toluene results in the clean formation of cis-Pt[(PyPP)H2]2Cl2 from cis-Pt(DMSO)[(PyPP)H2]Cl2. (H. Yuan, L. Thomas, and L. K. Woo, “Synthesis and Characterization of Mono-, Bis-, and Tetrakis-pyridyltriarylporphyrin Pd(II) and Pt(II) Supramolecular Assemblies. Molecular Structure of a Pd-Linked Bisporphyrin Complex,” Inorg. Chem. (1996) vol. 35, pp. 2808-2817.)
Drain and coworkers have reported a discrete supramolecular array of nine porphyrins (freebase or metallated with Zn2+ ions) by titration of PdCl2(NCPh)2 into a solution of monopyridyl triphenyl porphyrin, dipyridyl diphenyl porphyrin, and tetrapyridyl porphyrin (4:4:1) in toluene, mineral oil, or chloroform. (C. M. Drain, F. Nifiatis, A. Vasenko, and J. D. Batteas, “Porphyrin Tessellation by Design: Metal-Mediated Self-Assembly of Large Arrays and Tapes,” Angew. Chem. Int. Ed. (1998) vol. 37, pp. 2344-2347.)
Carlucci and co-workers report the formation of [Ag4(H2ttpyp)3](NO3)4.x solvent, [Ag2(H2ttpyp)3(NO3)](NO3).x solvent, and [Ag8(Zntpyp)7(H2O)2](NO3)8.x solvent by diffusing AgNO3 dissolved in N,N′-dimethylacetamide (DMA) into a tetrachloroethane/methanol (TCE/MeOH) solution of the free base or Zn2+-substituted tetra pyridyl porphyrin (TPyP). (L. Carlucci, G. Ciani, D. M. Proserpio, and F. Porta, “Open Network Architectures from the Self-Assembly of AgNO3 and 5,10,15,20-Tetra(4-pyridyl)porphyrin (H2tpyp) Building Blocks: The Exceptional Self-Penetrating Topology of the 3D Network of [Ag8(ZnIItpyp)7(H2O)2](NO3)8,” Angew. Chem. Int. Ed. (2003, vol. 43, pp. 317-322.)
Shelnutt et al. (“Dendritic Metal Nanostructures,” filed Jul. 8, 2004, “U.S. patent application Ser. No. 10/887,535) describes the deposition of metal dendrites on the surface of a surfactant structure template, such as a micelle, a liposome, a vesicle, or a membrane.
Shelnutt et al. describes the formation of porphyrin nanotubes that are not coordination polymers (“Heteroporphyrin Nanotubes and Composites,” U.S. Pat. No. 7,132,163 and “Heteroporphyrin Nanotubes and Composites,” U.S. Pat. No. 7,223,474).